Catalyst



Patented May 4, 1937 PATENT OFFICE CATALYST Edward S. Johnson, New Rochelle, N. Y., assignor to The'Calco Chemical Co., Inc., Bound Brook, N. J., a corporation of Delaware No Drawing. Application February 13, 1935, Serial No. 6,397

Claim.

pregnated with a catalytic material and thenv formed into pellets; second, massive fragments of various inert materials, such as for example diatomite brick fragments suitably calcined in .5 order to remove their friability; and third type various gels. a

Commercial silica gel has been tried but has proved a poor carrier for vanadium catalysts. A

series of gels having base exchange properties,-

such as zeolites and non-silicious base exchange bodies, have found extensive commercial use and are described forexample in patents to A. O. Jaeger, 1,657,754, 1,675,308, 1,675,309 and 1,694,123. These'gel carriers while highly effective by reason of their microporous structure have, in some cases, contained too much alkali and are relatively expensive.

In my co-pending application Serial No. 687,010, filed Aug. 26, 1933, I have described and 30 claimed a new silica gel prepared in an alkaline instead of an acid medium. According to the present invention, I have found that this alkaline silica gel which has beenprepared under conditions nonacid to Congo constitutes a carrier of particularly for vanadium catalysts for the contact sulphuric acid process. The efiiciency of vanadium catalysts mounted on or impregnated in fragments of this alkaline. silica gel far sur- 4() passes the efiiciency of vanadium catalysts on ordinary silica gel obtained in an acid medium and the catalysts produced are equal to the best base exchange catalysts.

The alkalinesilica gel may be prepared according to any of the examples of my co-pending application above referred to, but in general two main precautions have to be adopted. First, the temperature has to be kept low, preferably about 0 C. and second the potassium or sodium silicate solution used as a raw material must be diluted.

The gel after preparation and removal of mother liquor may be treated with suitable catalyst solutions or it may first be dried. When the gel is dried its absorptive powers are very high, 5 but in many cases all of the catalyst solution extraordinary efiiciency for vanadium catalysts must be introduced in 'a single impregnation otherwise if a second impregnation is tried the gel tends to shatter and disintegrate into sand-like particles. When, however, the gel is not completely dried prior to impregnation, the impregnation may take place in two stages and for catalysts whichare to carry a maximum of vanadium this procedure has advantages, although it suffers from the disadvantage of being more time consuming and requiring two treatments instead of one, thus increasing the cost of the final catalyst. Both modifications are included in the present invention and the particular modification to be chosen in any given instance will be dictated by the technical requirements, costs, etc.

Impregnation may be with any suitable solution of a vanadium compound, but for most purposes it is desirable to introduce the vanadium in the form of ammonium vanadatein which form it is cheaply obtainable on the market. Other forms of soluble vanadium compounds, such as vanadyl sulphate, may, of course, be employed wherever desired.

When the catalyst is to be used for the contact sulphuric acid process or for certain delicate organic oxidations, a promoter is required in the first case and a stabilizer in the second. The best promoters for the contact sulphuric acid process are compounds of potassium, caesium, rubidium and thallium. Compounds of sodium while having promoting action are less effective. For stabilization in certain organic reactions the alkali metals are more or less interchangeable and for certain other organic reactions permitting a more active catalyst, such as for example the catalytic oxidation of naphthalene, compounds of other metals, such as copper, silver and the like, are effective.

The high porosity of the alkaline silica gel carrier of the present invention may be considered as a physical promoter and highly active catalysts are obtained with a minimum of vanadium. This is particularly true in the contact sulphuric acid process where the catalysts of the present invention find their most important field of usefulness. I

The invention will be described in greater detail in the following specific examples, which illustrate typical catalysts embodying various features of the invention.

Example I An alkaline silica gel is prepared by diluting 25 liters of a potassium silicate solution containing 21.8% SiOz and 10.5% KOH equivalent with 35 liters of water, cooling to C. and adding 14 liters of 13% sulphuric acid also cooled to 0 C. Vigorous agitation is maintained and care is taken to prevent local overheating. The gel rapidly sets to a clear or slightly turbid product and on standing begins to sweat, shrinks away from the reaction vessel and cracks open. After a number of hours, a mother liquor is formed and is poured oil. The gel is then permitted to stand for some time in order to age and partially dry and then is broken into suitable fragments and washed.

The gel thus prepared is treated with a solution of ammonium vanadate and potassium sulphate in the proportion of one moi. of vanadium to three of potassium. The gel absorbs the soluf tion, bleaching the yellow color, probably by-ad-v sorption of free vanadic acid After complete adsorption the liquor is removed and gel-dried resulting in slight flssuring. The catalyst is again treated with the vanadium-potassium solution and adsorbs a further amount of catalyst solution,

but the adsorption is not sufiiciently great'ito bleach the yellowish color. This is probably due Example II A gel as prepared in Example I is dried to about 25% of SiOz as against about 12 in the v gel of Example I. The gel fragments are soaked in a solution of ammonium vanadate and potassium sulphate containing 5% ammonium vanadate, 11% potassium sulphate and 84% of water. The'gel fragments are permitted to soak for 20-24 hours and are then dried. ,The absorption at the beginning is very rapid with evolution of gas from pores of the gel resultingv in suflicient effervescence to float the gel particles to the top of the solution. The yellowish color of the ammoniumvanadate-potassium sulphate solution is completely bleached, and practically no disintegration oi the gel is observable. When tested as a sulphuric acid catalyst the results were substantially as in Example I.

Example III A gel as prepared in Example I is dried at 21% Bio: at 60-70 C. It is then soaked for 12 hours in the ammonium vanadate-potassium sulphate solution and dried at 60-70 C. A saturated ammonium vanadate-potassium sulphate solution is then prepared and the gel soaked for a short time. The disintegration is only slight. The percent of vanadium adsorbed by the catalyst is about 3.75 and when tested, in the contact sulphuric acid process, conversions of over 98% are obtained at half commercial loadings even at 425 C. with similar conversion percentages at full commercial loading under the normal temperature gradient for sulphuric acid catalysis.

The catalyst described is also suitable for the catalytic oxidation of naphthalene to alpha'napthaquinone when the catalyst used in a bath cooled converter where careful temperature control is assured. 1

Example IV 200 liters of a commercial sodium silicate solution of the usual strength, about 30 B. are diluted with 480 liters of water and cooled approximately 0 C. Care should be taken not to go much below 0 C. as there is danger of sodium silicate crystallizing out. 204 liters of 13% sulfuric acid are cooled at 0 C. and stirred into the diluted sodium silicate solution, the whole being maintained at the low temperature. In about 3 minutes the mixture becomes cloudy and at the end of 6 minutes the gel sets.

After standing sufficiently the mother liquor is poured off and after aging and partially drying the gel is broken into suitable fragments and washed. This gel is treated as described in Example III above and a catalyst is obtained which has substantially the same activity in the contact sulphuric acid process.

Example V A catalyst is prepared as described in Example III, but instead of using potassium sulphate an equivalent amount of rubidium or caesium sulphate is used. The catalyst obtained shows somewhat higher activity at low temperatures giving 98% or over at loadings substantially up to commercial.

The term silica gel is used to cover a gel con sisting substantially of SiO2 or silicic acid. It does not include any base exchanging polysilicates which are not substantially silica or silicic acid.

I claim:

1. A catalyst for vapor phase catalytic oxidations comprising a vanadium compound carried by massive fragments of a microporous silica gel which is obtained by the acidification of alkali metal silicate solutions under conditions which are non-acid to Congo.

2. A catalyst for catalytic vapor phase oiddations according to claim 1 in which the vanadium compound is associated with a promoter.

3. A catalyst for the catalytic vapor phase oxidations according to claim 1 in which the vanadium compound is associated with the compound of an element included in the group consisting of potassium, rubidium, caesium and thallium.

4. A catalyst for the catalytic vapor phase oxidations according to claim 1 in which the vanadium compound is associated with the compound of an element included in the group consisting of potassium, rubidium, caesium and thallium, the molecular proportion of the vanadium compound to the other compound being approximately 1 to 3.

5. Acatalyst for the catalytic vapor phase oxidations comprising vanadic oxide associated with potassium sulphate on a carrier consisting of massive fragments of microporous silica gel obtained by acidification of an alkaline metal silicate under conditions which are at all times non acid to Congo.

6. A catalyst according toclaim 5 in which the molecular proportion of vanadic acid to potassium sulphate is approximately '1 to 3.

7. A method of producing a catalyst for vapor phase catalytic oxidations; which comprises preparing massive fragments of a microporous silica gel by the acidification of alkali metal silicate. under conditions which are at all times non-acid to Congo, drying said gel to an SlOz content about 20% and subjecting the gel fragments to the action of a solution of a vanadium compound and a compound of an element included in the class consisting of potassium, rubidium, caesium and thallium, and drying the impregnated gel.

8. A method of preparing a catalyst according to claim 7 in which the solution of ammonium vanadate and potassium sulphate is in the moing the impregnated gel fragments and subjectlecular proportion of approximately 1 to 3. ing them to a second impregnation of a similar 9. A method of producing a catalyst for vapor solution, the concentration of which is high phase catalytic oxidations which comprises preenough to prevent disintegration of the gel tragparing massive fragments of a microporous silments and again drying the gel fragments. 5 ica gel obtained by acidification of an alkali metal 10. A method of preparing a catalyst accordsilicate under conditions which are at all times ing to claim 9 in which the solution is of amnon-acid to Congo, and subjecting said fragmonium vanadate and potassium sulphate in apments without drying to an $10: content mateproximate proportion of one mol. of ammonium iu riaily in excess of 21% to impregnation by a soiuvanadate to three mols of potassium sulphate. 10

tion of a vanadium compound and a compound or an element included in the group consisting of EDWARD S. JOHNSON. potassium, rubidium, caesium and thallium, dry 

